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US8173440B2 - Nanoporous material for aldehydes with direct optical transduction - Google Patents

Nanoporous material for aldehydes with direct optical transduction Download PDF

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US8173440B2
US8173440B2 US12/066,616 US6661606A US8173440B2 US 8173440 B2 US8173440 B2 US 8173440B2 US 6661606 A US6661606 A US 6661606A US 8173440 B2 US8173440 B2 US 8173440B2
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aldehyde
formaldehyde
metal oxide
corresponds
probe molecule
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US20080220534A1 (en
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Hélène Paolacci
Thu-Hoa Tran-Thi
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L'UNIVERSITE PARIS SUD (PARIS XI)
Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Universite Paris Saclay
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Commissariat a lEnergie Atomique CEA
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/200833—Carbonyl, ether, aldehyde or ketone containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25375—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
    • Y10T436/255—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.] including use of a solid sorbent, semipermeable membrane, or liquid extraction

Definitions

  • the present invention relates to the field of the metrology of aldehydes, for example in contaminated environments, and also to the pollution control of said environments.
  • the environment may be an exterior or interior (e.g. domestic) atmosphere, contaminated or uncontaminated by at least one aldehyde, preferably formaldehyde.
  • It also relates to a method for detecting and/or quantifying and/or trapping at least one gaseous aldehyde, especially formaldehyde, based on measurements of the variation of at least one physicochemical property of said material.
  • aldehyde denotes any organic molecule having a terminal carbonyl functional group preferably chosen from formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, acrolein, pentanal, hexanal and benzaldehyde.
  • Aldehydes are among the most abundant domestic chemical pollutants. Their sources are extremely numerous. These sources may be, in particular, connected to an external production such as the photooxidation of methane. However, the main sources for the release of aldehydes are found inside dwellings and are very diverse:
  • Formaldehyde is also a preservative, disinfectant and desiccant. For these reasons, it is widely used as a solvent in hospital surroundings for disinfecting surgical instruments and also in the funeral service industry where embalming is carried out.
  • Formaldehyde is the most studied of aldehydes as it is widely used in the manufacture of very many construction products and various equipment.
  • the release of formaldehyde varies depending on the temperature and humidity conditions. Its pungent odor is detected by a person at low concentrations (from 0.048 to 0.176 ppm or from 0.06 to 0.22 mg/m 3 ).
  • Exposure to formaldehyde causes irritation which is experienced by most of the population at concentrations between 1 and 3 ppm, this irritation being rapidly aggravated when the content rises. Most individuals cannot, in effect, tolerate a prolonged exposure at 4-5 ppm. At 10-20 ppm, signs of severe irritation of the ocular mucous membranes and airways occurs from the start of exposure.
  • the detection methods that are already commercially available are based on trapping aldehydes by reaction with a suitable molecule, then analyzing them by gas or liquid chromatography.
  • the aldehyde is trapped on an absorber or a solid support (silica or octadecyl-grafted silica) impregnated with a reactant such as 2,4-dinitrophenylhydrazine (DNPH) or 2-hydroxymethylpiperidine, capable of reacting with the aldehyde to form a product, a hydrazone or an oxazolidine.
  • a reactant such as 2,4-dinitrophenylhydrazine (DNPH) or 2-hydroxymethylpiperidine
  • DNPH 2,4-dinitrophenylhydrazine
  • 2-hydroxymethylpiperidine capable of reacting with the aldehyde to form a product, a hydrazone or an oxazolidine.
  • the NIOSH 2451 method consists of a take-up of formaldehyde on a solid absorbent impregnated with 2-hydroxymethylpiperidine, followed by a gas chromatography analysis. The detection limits of this method are from
  • Nash was the first to identify a mixture of reactants capable of reacting specifically in solution with formaldehyde. These reactants are a ⁇ -diketone, for example acetylacetone and ammonium acetate. They give rise to the formation of a highly fluorescent derivative, 3,5-diacetyl-2,6-dihydrolutidine (DDL) [Nash T., Biochem. J., 55, 416, (1953)].
  • DDL 3,5-diacetyl-2,6-dihydrolutidine
  • Sawicki et al. then extended this reaction to other ketones such as dimedone [Sawicki E. et al., Mikrochim. Acta, 148, (1968); Sawicki E. et al., Mikrochim. Acta, 602, (1968)].
  • the final product is 3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8,9,10-decahydro-1,8-acridinedione, whose
  • Detection methods based on mixed solid/liquid trapping systems and using Fluoral-P have been developed.
  • One of these systems uses methods of injection of Fluoral-P and formaldehyde in a liquid stream followed by retention of the product formed on a grafted silica support of C18 type impregnated with the elution solvent.
  • the analysis is carried out by absorbance or by fluorescence [Teixera, L. S. G., et al., Talanta, 64 (2004) 711-715]
  • This method has the disadvantage of being relatively sensitive to the degree of ambient humidity and to temperature. Specifically, the measurements are impaired when the degree of humidity is outside of a range of 30-700, and/or when the temperature exceeds 35° C. Furthermore, after keeping for more than six months, a reduction in the sensitivity of the impregnated paper is observed.
  • the presence of silica granules which have the particularity of attracting and maintaining the humidity by capillary action makes it possible to explain, at least partly, the fact that the degree of ambient humidity influences this method.
  • WO 2004/10457.3 describes a sensor capable of detecting formaldehyde in an atmosphere, consisting of a generally polysaccharide gel based, for example, on xanthan gum or gum Arabic, pectin, starch, agar or alginic acid, the gel comprising a Schiff base such as pararosaniline, sulfuric acid or one of its salts, another acid to adjust to pH 3 and water.
  • a generally polysaccharide gel based, for example, on xanthan gum or gum Arabic, pectin, starch, agar or alginic acid
  • the gel comprising a Schiff base such as pararosaniline, sulfuric acid or one of its salts, another acid to adjust to pH 3 and water.
  • U.S. Pat. No. 6,235,532 describes a method of detecting 2-furaldehyde in oil using aniline acetate. The detection is carried out using a porous sol-gel, especially methyltrimethoxysilane, matrix containing aniline acetate.
  • One of the main problems of the methods of the prior art is that they do not allow the direct and in situ detection and/or quantification of formaldehyde or of other aldehydes in gas form irrespective of the conditions of the environment.
  • Certain methods of the prior art require the withdrawal of samples and the trapping of the gas in liquid/solid phase to enable a qualitative and/or quantitative analysis.
  • Other methods of the prior art are highly sensitive to the degree of ambient humidity or to temperature.
  • One subject of the present invention is therefore a method for detecting and/or assaying and/or trapping at least one aldehyde, preferably formaldehyde, which comprises a step of bringing a gas stream into contact with a material comprising a nanoporous metal oxide sol-gel matrix, said matrix containing at least one probe molecule bearing at least one reactive functional group which can react with an aldehyde functional group.
  • the aldehyde is chosen from formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, acrolein, pentanal, hexanal and benzaldehyde.
  • gas stream is understood to mean both a gaseous atmosphere or a mixture of gases.
  • nanoporous is understood to mean a porous system with pore diameters of less than 100 nm.
  • method of trapping is understood to mean a pollution-control or decontamination method which makes it possible to capture the aldehyde and thus to purify a contaminated environment.
  • probe molecule denotes any organic molecule bearing a reactive functional group whose reaction with an aldehyde functional group leads to a modification of at least one of its physicochemical properties detectable by a suitable analysis technique, preferably a modification of its spectral properties detectable by spectrophotometry.
  • the probe molecule before and/or after reaction with an aldehyde is characterized by spectral properties, especially absorption and/or fluorescence spectra, the variation of which is detectable by a suitable spectrophotometric method known to a person skilled in the art.
  • the probe molecule may be a chromophore whose absorption and/or fluorescence spectra are modified by reaction with an aldehyde.
  • the expression “variation of the absorption and/or fluorescence spectrum” is understood to mean a shift in the wavelength of the absorption and/or fluorescence maxima, or optionally a loss or gain in the absorption or fluorescence intensity at a given wavelength.
  • the method additionally comprises a step of analyzing the variation of the spectral properties of at least one probe molecule of the material, for example by at least one spectrophotometry technique.
  • the method according to the invention therefore takes advantage of the spectral properties of the probe molecules that have reacted with at least one aldehyde. For this, it is desirable to expose the material to the environment to be tested, said material being advantageously deposited on a suitable substrate.
  • the absorbance and/or fluorescence spectra of the probe molecule before and after possible reaction with the aldehyde will advantageously be compared to determine the presence or absence and/or the amount of aldehyde present in the environment tested.
  • the method also makes it possible to analyze the overall spectral variations in the material during the reaction of the probe molecule with at least one aldehyde.
  • a person skilled in the art will choose to determine the variation of the fluorescence or that of the absorbance as a function of the aldehyde to be detected and/or quantified.
  • probe molecules excited by light irradiation, in proximity to a thin layer of metal may be coupled to the surface plasmons and lead to lower detection limits and make it possible to thus detect or assay smaller amounts of aldehyde.
  • the material before and/or after reaction with an aldehyde is characterized by its interaction with Love type waves.
  • the structural modifications linked to the reaction of the probe molecules with the aldehydes result, in particular, in a variation in mass, viscoelasticity, or else dielectric constant which has an impact on the Love waves.
  • This embodiment is generally implemented in the presence of a piezoelectric material or a material on which it is possible to detect and generate Love waves, typically using electrodes made of interdigitated combs in a delay line or resonator configuration.
  • the probe molecule bearing a functional group reactive with an aldehyde functional group is chosen from enaminones and the corresponding ⁇ -diketone/amine pairs thereof, imines and hydrazines, or salts derived from these compounds.
  • the probe molecule incorporated into the material of the method according to the invention is an enaminone.
  • enaminone is understood to mean any molecule which corresponds to the formula (I):
  • R 1 corresponds to a hydrogen, an alkyl or aryl radical
  • R 2 corresponds to a hydrogen
  • R 3 corresponds to a hydrogen, an alkyl or aryl radical
  • R 4 corresponds to a hydrogen, an alkyl or aryl radical
  • R 5 corresponds to a hydrogen
  • An alkyl radical may optionally be monosubstituted or polysubstituted, linear, branched or cyclic, saturated or unsaturated, a C 1 -C 20 , preferably C 1 -C 10 alkyl radical, the substituent or substituents possibly containing one or more heteroatoms such as N, O, F, Cl, P, Si or S.
  • alkyl radicals mention may especially be made of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl radicals.
  • An aryl radical may be an aromatic or heteroaromatic, monosubstituted or polysubstituted carbon-based structure composed of one or more aromatic or heteroaromatic rings each comprising from 3 to 8 atoms, the heteroatom possibly being N, O, P or S.
  • the substituents may be different from one another.
  • substituents of the alkyl and aryl radicals mention may especially be made of halogen atoms, alkyl, haloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, amino, cyano, azido, hydroxy, mercapto, keto, carboxy, etheroxy and alkoxy, such as methoxy, groups.
  • R 1 and R 3 are independently a methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl or phenyl radical and R 4 a hydrogen
  • R 1 is a methyl radical
  • R 2 a hydrogen
  • the detection may advantageously be carried out by measuring the variation of the absorbance at a wavelength of 415 nm, at which only the DDL absorbs.
  • DDL has fluorescence properties
  • its detection and its assaying may be carried out by exciting it, especially at 415 nm, and by measuring the fluorescence intensity at a given wavelength ( ⁇ max of fluorescence at 502 nm) or the total fluorescence (integrated over the entire spectrum) as a function of time.
  • the ⁇ -diketone/amine pair corresponding to the enaminone described previously may also be considered as a probe molecule in its own right.
  • the enol form of the ⁇ -diketone is considered as an equivalent form; it is customary, in effect, to find a thermodynamic equilibrium between these two forms. Since the reaction mechanisms are not exactly elucidated, it appears that a ⁇ -diketone/amine pair corresponding to the enaminone described previously will react with an aldehyde, and preferably with formaldehyde.
  • the expression “ ⁇ -diketone/amine pair” is understood to mean any pair of molecules which corresponds to the formula (II):
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meaning already given above, the amine possibly being replaced by its corresponding ammonium salt.
  • the amine may be quaternized and then the counterion may be chosen from the counterions known to a person skilled in the art and that are most suitable for the reactants.
  • the counterion may be chosen from the counterions known to a person skilled in the art and that are most suitable for the reactants.
  • the preferred ammonium salts mention may especially be made of acetates, sulfates, halides, and particularly chlorides and tetrafluoroborates.
  • At least one imine is incorporated, as a probe molecule, into the material of the method according to the invention.
  • the chosen imine may be, for example, fuchsin or pararosaniline, advantageously the imine will be chosen from Schiff bases and more particularly from acridine yellow, methyl yellow or dimethyl yellow.
  • hydrazine is incorporated into the material of the method according to the invention.
  • the term “hydrazine” is understood to mean any molecule which corresponds to the formula (III):
  • R 6 corresponds to a hydrogen, a C 1 -C 20 , preferably C 1 -C 10 , alkyl radical, more preferably a methyl, ethyl, isopropyl, butyl, isobutyl, text-butyl and pentyl radical, a C 3 -C 16 aryl radical, especially a phenyl and arylsulfonyl radical; and R 7 corresponds to a C 3 -C 16 aryl radical, especially a phenyl and arylsulfonyl radical.
  • the hydrazine of the material according to the invention is chosen from 2,4-dinitrophenylhydrazine (DNPH), 2-hydrazinobenzothiazole, 3-methyl-2-benzothiazolinone, 5-(dimethylamino)naphthalene-1-sulfonylhydrazine, 1-methyl-1-(2,4-dinitrophenyl)hydrazine, N-methyl-4-hydrazino-7-nitrobenzofurazan and hydralazine.
  • DNPH 2,4-dinitrophenylhydrazine
  • 2-hydrazinobenzothiazole 3-methyl-2-benzothiazolinone
  • 5-(dimethylamino)naphthalene-1-sulfonylhydrazine 1-methyl-1-(2,4-dinitrophenyl)hydrazine
  • N-methyl-4-hydrazino-7-nitrobenzofurazan N-methyl-4-hydrazino-7-nitrobenzofurazan
  • nanoporous metal oxide sol-gel matrix is understood to mean a nanoporous polymeric network produced from at least one metal oxide of formula (IV): M(X) m (OR 8 ) n (R 9 ) p in which: M corresponds to a metal chosen from silicon, aluminum, titanium, zirconium, niobium, vanadium, yttrium and cerium; R 8 and R 9 correspond independently to an alkyl or aryl radical such as defined above; n, m and p are integers, such that their sum is equal to the valency of M and that n is greater than or equal to 2; and X is a halogen, preferably chlorine.
  • the metal M of the oxide that is a precursor of the sol-gel matrix is silicon or zirconium.
  • the metal oxide is Si(OMe) 4 .
  • the inventors have demonstrated that the choice of the metal oxide forming the porous matrix conditions the size of the pores and the accessibility of the aldehydes to the probe molecules.
  • the size of the pores will advantageously be larger in order to facilitate the dispersion of the gaseous medium within the matrix.
  • p be at least equal to 1.
  • the inventors have developed novel materials capable of reacting with at least one aldehyde. This is why another subject of the present invention is a material capable of reacting with at least one gaseous aldehyde comprising a nanoporous sol-gel matrix containing at least one probe molecule bearing a functional group reactive with an aldehyde functional group.
  • the material is characterized as indicated above.
  • the radicals R 8 and R 9 of the metal oxide that is a precursor of the nanoporous sol-gel matrix are independently methyl or ethyl radicals and the probe molecule is an enaminone.
  • the material according to the invention comprises, as a metal oxide, a polymer of SiO 2 advantageously prepared from Si(OMe) 4 , and Fluoral-P as a probe molecule.
  • a material is particularly advantageous for the specific detection and/or assaying of gaseous formaldehyde.
  • the invention also relates to a process for preparing the above material comprising:
  • the sol-gel matrix of the material according to the invention may be produced according to a sol-gel process.
  • sol-gel process are techniques which make it possible, by simple polymerization of molecular precursors, especially including metal oxides, to obtain polymeric matrices at temperatures close to ambient temperature (20 to 35° C.)
  • the chemical reactions, i.e. hydrolysis and condensation, that are the basis of sol-gel processes, are started when the molecular precursors are brought into the presence of water: the hydrolysis of the oxides takes place first, then the condensation of the hydrolyzed products leads to gelling of the matrix.
  • the step of producing the porous sol-gel matrix (a) comprises a step of hydrolyzing at least one metal oxide, said hydrolysis step preferably being carried out in the presence of an organic solvent, such as an alcohol, for instance methanol or ethanol.
  • an organic solvent such as an alcohol, for instance methanol or ethanol.
  • the hydrolysis step is carried out at a pH below 7 using an inorganic acid such as HCl or H 2 SO 4 .
  • the hydrolyzed products react together to form polymers which do not stop growing until a three-dimensional polymeric network is obtained.
  • the metal oxide clusters remain in suspension without precipitating; this is the sol. These clusters gradually occupy an increasing large volume fraction. The viscosity then becomes high and the liquid finishes by gelling into a matrix.
  • the matrix thus obtained is therefore composed of a polymeric network which has a porosity that can be varied.
  • the diameter of the pores of the sol-gel matrix may also be adjusted by choosing particular metal oxides.
  • the inventors especially consider that metal oxides of formula (IV) for which R 8 and R 9 are alkyls, preferably methyl or ethyl radicals, make it possible to create matrices whose pores have a reduced diameter.
  • R 8 and R 9 are alkyls, preferably methyl or ethyl radicals.
  • the step of producing the sol-gel matrix (a) and that of incorporating at least one probe molecule (b) will be carried out simultaneously. This is because the preparation conditions are gentle enough for the probe molecules to be incorporated into the sol-gel matrix without being altered.
  • the method according to the invention additionally comprises a homogenization and/or drying step.
  • the drying step enables, amongst other things, the evaporation of the water and of the alcohols of the matrix.
  • the incorporation of at least one probe molecule could be carried out in the nanoporous matrix either by impregnation in solution or in the vapor phase according to techniques that are well known to a person skilled in the art, especially including sublimation.
  • the material according to the invention may be integrated in devices or sensors.
  • the present invention therefore also relates to any device or sensor specific to gaseous aldehydes, preferably formaldehyde, characterized in that it comprises at least one material conforming to the invention or obtained according to the preparation method conforming to the invention.
  • a sensor comprises at least one material conforming to the invention deposited on a suitable substrate, preferably in the form of a thin film on a transparent substrate.
  • the substrate may be chosen from those commonly used in the field of spectrophotometric analysis, especially including slides or plates made of glass, quartz, mica or fluorspar.
  • the deposition is carried out according to techniques well known to a person skilled in the art including, in particular, dip coating, spin coating or (liquid or gas) spraying.
  • the deposition of the material according to the invention is carried out by dip coating.
  • a person skilled in the art will adjust the rate of removal of the substrate from the deposition of the material which is deposited, preferably a rate close to 25 mm/min.
  • the dip coating may be carried out at ambient temperature (22-25° C.) with a relative humidity of the air between 15 and 50%.
  • the devices or sensors integrate at least one source of light excitation ( 10 ) and a collector ( 11 ). They are composed of a first compartment ( 4 ) and a second compartment ( 5 ) and a screen ( 7 ).
  • the gas is introduced into the sensor via a specific inlet ( 1 ) then passes through a thermostat which makes it possible to control the temperature, and also a particulate filter ( 3 ).
  • a delivery pump system ( 8 ) makes it possible to accelerate the diffusion of the gas to the material according to the invention ( 9 ).
  • the pump may be placed near the gas outlet ( 2 ) rather than close to the inlet, in this case a micropump will advantageously be used.
  • the material according to the invention ( 9 ) is protected from the outside by a protective envelope ( 13 ) in a leaktight manner by an o-ring ( 12 ).
  • a protective envelope ( 13 ) in a leaktight manner by an o-ring ( 12 ).
  • the reaction of the aldehyde with the probe molecule will be detected after light excitation ( 10 ) by a collector ( 11 ) and read on the screen ( 7 ).
  • the light source will be composed of a halogen lamp or a light-emitting diode and the collector of a diode strip or a low-voltage photomultiplier.
  • the detection method is based on a variation in absorbance of the doped film
  • the photons, by rebonding multiple times off the film-covered walls, will be strongly absorbed by the material ( FIG. 11 ).
  • a gas outlet ( 2 ) is provided in the frame of this sensor.
  • Miniaturized devices or sensors are preferred. It is desirable that the device or sensor comprises, in addition, a support for the materials according to the invention, more particularly a support that accommodates the chosen substrate as a function of the detection method.
  • the device or sensor will also comprise a system for accelerating the diffusion of the medium to be analyzed, particularly a gaseous medium.
  • the system for accelerating the diffusion of the gas is a pneumatic system such as a piston, a delivery pump or a micropump.
  • a pneumatic system such as a piston, a delivery pump or a micropump.
  • Such a system will be particularly useful in the case of a pollution-control device.
  • the invention thus particularly relates to aldehyde sensors with direct optical transduction.
  • a device that makes it possible to benefit from the surface plasmons will contain, for example, a sheet chosen from the substrates commonly used in the field of spectrophotometric analysis, especially including slides or plates made of glass, quartz, mica or fluorspar, said plate being covered with a layer of metal on which the material according to the invention is deposited.
  • the choice of metal is generally linked to that of the probe molecule; thus, for example, for UV-absorbing probe molecules it is preferable to use aluminum which has a UV emission linked to the plasmons [J. Phys. Chem. B, 2004, 108, 19114-19118].
  • the thickness of the metal layer may be between 10 and 90 nm, preferably around 60 nm. It is advantageous to deposit a layer of material that is free from the probe molecule between the layer of metal and the layer of material in order to prevent a probe molecule from being in direct contact with the metallized surface.
  • the layer of material will have a thickness between 5 and 40 nm, preferably around 25 nm, and the layer of material that is free from the probe molecule will have a thickness between and 20 nm, preferably 10 nm.
  • the irradiation wavelength will depend on the nature of the metal and on the fluorescent probe molecule.
  • UV sources 260-300 nm for Al films and 350-400 nm for Ag films
  • the variations in the mass, viscoelasticity or dielectric constant of the material are studied using Love type waves, especially by the variation in their phase velocity or their propagation velocity.
  • Electrodes with interdigitated comb structures may be positioned at the two ends of the substrate surface and the nanoporous material is positioned in the free space between the two electrodes, according to a “delay line” configuration.
  • Love type waves may then be generated by the transducers and the variation in their propagation velocity may, for example, be monitored by the transducers.
  • the piezoelectric substrate equipped with transducers could be covered by a guide coat, for example made of SiO 2 , and the nanoporous material deposited on the surface of this guide coat.
  • the material according to the invention has numerous advantages which enable it to be used in the metrology of gaseous aldehydes, and more particularly of gaseous formaldehyde, and also in pollution control. Due to its preparation method, the material according to the invention is nanoporous and therefore offers a very large specific surface area for adsorption. This structural characteristic is even more important in the context of the pollution-control device. Furthermore, the size of the pores and the nature of the material according to the invention may easily be adjusted for selectively detecting and/or assaying certain aldehydes, especially including formaldehyde.
  • the material according to the invention may be used in the methods for detecting and/or assaying and/or trapping gaseous aldehydes irrespective of the conditions, especially including the degree of ambient humidity.
  • the invention does not require the presence of acid nor working at a particular pH.
  • the invention may be implemented between pH 4 and 10, especially between pH 4 and 7.
  • the material according to the invention may easily be integrated into a sensor or a device which allows in situ, direct and simple detection of gaseous aldehydes
  • sensors may be used in a network and to permanently ensure the quality control of an environment at high risk of contamination by aldehydes.
  • the devices or sensors may also be combined with a visual or audible alarm which is activated when the aldehyde content in the environment to be tested reaches a certain critical threshold.
  • FIG. 1( a ) represents an absorbance spectrum (in arbitrary units a.u.) as a function of the wavelength (nm) observed over time during exposure of a porous film containing Fluoral-P to a nitrogen stream containing 8 ppb of formaldehyde with a relative humidity of the gas mixture of 58%
  • FIG. 1( b ) represents a curve illustrating the variation in absorbance of Fluoral-P (at 300 nm) and of DDL (at 415 nm) as a function of the exposure time (in min).
  • FIG. 2 represents a fluorescence spectrum as a function of the wavelength (nm) of 3,5-diacetyl-2,6-dihydrolutidine (reaction product of Fluoral-P with formaldehyde) measured at the end of the experiment when the absorbance at 415 nm reaches a plateau.
  • the fluorescence intensity is measured as the number of counts per second (cps).
  • FIG. 3 represents a curve illustrating the variation in the absorbance (a.u.) at 415 nm as a function of the concentration (in parts per billion, ppb) of 3,5-diacetyl-2,6-dihydrolutidine measured after complete consumption of the Fluoral-P, the velocity of the gas stream is 200 ml/min and the relative humidity is 58%.
  • FIG. 4 represents the variation in the fluorescence intensity (cps) of 3,5-diacetyl-2,6-dihydrolutidine at 510 nm as a function of its absorbance (a.u.) at 415 nm; the values were obtained from the exposure, in a stream, of various films containing Fluoral-P for various formaldehyde contents in nitrogen with a relative humidity maintained at 58% and a gas stream of 200 ml/min for all the experiments.
  • cps fluorescence intensity
  • FIG. 6 represents the variation in the differential absorbance (a.u.) as a function of the wavelength (nm) during the exposure of a thin porous film containing 2,4-dinitrophenylhydrazine to a mixture of nitrogen containing 800 ppb of formaldehyde, the relative humidity is maintained at 58% and the gas stream is 200 ml/min.
  • FIG. 7 corresponds to a list of probe molecules which can be used within the context of the invention.
  • FIG. 8 corresponds to the diagram of a sensor according to the invention.
  • FIG. 9 represents a top view of compartment ( 4 ) of a sensor according to the invention.
  • FIG. 10 corresponds to a transverse cross section of compartment ( 4 ) comprising a material according to the invention.
  • FIG. 11 represents a detection system integrated into a sensor comprising two films composed of the material.
  • the spectrophotometric measurements were carried out on a UNICAM 500 spectrophotometer and a SPEX-FLUOROLOG 3 spectrofluorometer.
  • Fluoral-P could be synthesized according to the method developed by Lacey. [Lacey, Aust. J. Chem., 23 (1970) 841-842]. For the set of formaldehyde exposure experiments, the velocity of the gas stream was kept equal to 200 ml/min unless specified otherwise.
  • Fluoral-P incorporation of Fluoral-P into the porous matrices based on a metal oxide was carried out according to the “one-pot” method of the sol-gel process.
  • a matrix according to the invention was produced from tetramethoxysilane (TMOS) in an ethanol/water solution. The TMOS/ethanol/water molar proportions were equal to 1/4/4.
  • TMOS tetramethoxysilane
  • HCl aqueous solution of acid
  • a thin homogeneous film of the material prepared in Example 1 was then deposited on a quartz substrate (0.8 ⁇ 0.1 ⁇ 15 mm) by the dip-coating method with a film removal rate of around 25 mm/min.
  • the deposition was carried out at ambient temperature (22-25° C.) with a relative humidity of 15 to 50%.
  • the deposit (30 nm) could also be obtained in a similar manner on a quartz substrate previously coated with a layer of silver or aluminum (60 nm) and a layer of matrix according to the invention was produced from tetramethoxysilane (TMOS) (10 nm) in order to carry out a study using plasmons.
  • TMOS tetramethoxysilane
  • the sample was then placed in a flow cuvette (10 ⁇ 10 ⁇ 40 mm) having four optical faces equipped with a 4 mm diameter tubular outlet and inlet.
  • the gas mixtures were generated from a permeation oven containing a permeation tube filled with paraformaldehyde (solid trimer of formaldehyde) which was heated at 90° C. to release the formaldehyde vapors which were carried by nitrogen.
  • the initial content of formaldehyde in a 125 ml/min stream was 4 ppm.
  • the concentration and the flow of the final mixture were controlled and adjusted by a dilution system. Similar, the relative humidity of the mixture could be varied by injection of water vapor adjusted using a flowmeter.
  • DDL had fluorescence properties
  • its detection and therefore the assaying of formaldehyde could be carried out by illuminating the film, especially at 415 nm, so as to excite the DDL and by collecting the fluorescence intensity at a given wavelength ( ⁇ max of fluorescence at 502 nm) or the total fluorescence (integrated over the entire spectrum) as a function of time.
  • the fluorescence spectrum from FIG. 2 corresponded to the end of the exposure when all the Fluoral-P had reacted.
  • the response time of the analysis is limited here by the experimental dilution device which does not allow a flow rate of 200 ml/min to be exceeded. An increase of the flow rate to 1 or 2 l/min should reduce this time by a factor of 5 to 10.
  • the sensitivity can be greatly increased in the fluorimetric measurements, in particular, by exciting the 3,5-diacetyl-2,6-dihydrolutidine in the whole of its absorption band between 360 and 470 nm and by collecting the integrated fluorescence over the entire fluorescence spectrum.
  • optical interference filters for delimiting the excitation wavelength range and the emission collection range would make it possible to avoid using a spectrophotometer and therefore to reduce the cost of the detection equipment.
  • a thin homogeneous film of the material prepared in Example 4 was then deposited on a quartz substrate (0.8 ⁇ 0.1 ⁇ 15 mm) by the dip-coating method with a film removal rate of around 25 mm/min.
  • the deposition was carried out at ambient temperature (22-25° C.) with a relative humidity of 15 to 50%.
  • the 2,4-dinitrophenylhydrazine (DNPH) reacts with most aldehydes by forming the corresponding hydrazone derivative.
  • the material containing DNPH is non-selective and can therefore be used for a measurement of all of the aldehydes present in the air. Given the possibility of varying the pore size of the nanoporous material, it is possible to discriminate the aldehydes by their size in order to only detect small-size aldehydes (formaldehyde and acetaldehyde) It should be noted that small-size ketones (acetone) could interfere with this measurement.

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US9562882B2 (en) 2008-07-11 2017-02-07 Cea—Commissariat Atomique Et Aux Energies Alternatives Nanoporous detectors of monocyclic aromatic compounds and other pollutants
US8749792B2 (en) 2011-09-02 2014-06-10 Commissariat A L'energie Atomique Et Aux Energies Alternatives Device for optical measurement of materials, using multiplexing of light
US9046487B2 (en) 2011-09-02 2015-06-02 Commissariat à l'énergie atomique et aux énergies alternatives Device for lighting an object, with light source provided with a member for sampling a portion of said light, application to the measurement of flux variations of the source
US9427486B2 (en) 2013-06-28 2016-08-30 Seb S.A. Filter cartridge for an air purifier
CN104897659A (zh) * 2014-03-06 2015-09-09 苏州工业园区新国大研究院 甲醛气体浓度的检测方法
US20170296967A1 (en) * 2014-09-24 2017-10-19 Seb S.A. Filtration Device for Air Purification Appliance
US10561983B2 (en) 2014-09-24 2020-02-18 Seb S.A. Filtration device for air purification appliance

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CA2622487C (fr) 2014-08-26
US20080220534A1 (en) 2008-09-11
CA2622487A1 (fr) 2007-03-22
FR2890745A1 (fr) 2007-03-16
WO2007031657A2 (fr) 2007-03-22
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JP2009508134A (ja) 2009-02-26

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